Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols

Direct (utilize easily available and abundant precursors) and selective (both chemo- and regio-) aliphatic C–H functionalization is an attractive mean with which to streamline chemical synthesis. With many possible sites of reaction, traditional methods often need an adjacent polar directing group nearby to achieve high regio- and chemoselectivity and are often restricted to a single site of functionalization. Here we report a remote aliphatic C–H thiolation process with predictable and switchable regioselectivity through NiH-catalysed migratory hydrothiolation of two feedstock chemicals (alkenes/alkynes and thiols). This mild reaction avoids the preparation of electrophilic thiolation reagents and is highly selective to thiols over other nucleophilic groups, such as alcohols, acids, amines, and amides. Mechanistic studies show that the reaction occurs through the formation of an RS-Bpin intermediate, and THF as the solvent plays an important role in the regeneration of NiH species. Construction of C–S bonds via C–H functionalization is an attractive route to organosulfur compounds. Here, the authors show the synergistic combination of NiH-catalysed alkene isomerization and subsequent thiolation to afford remote hydrothiolation products from alkenes (or alkynes) and thiols under mild conditions.